EP2492273A1 - Dépôt de films minces contenant du gallium au moyen d'un précurseur de gallium alkylamide - Google Patents

Dépôt de films minces contenant du gallium au moyen d'un précurseur de gallium alkylamide Download PDF

Info

Publication number
EP2492273A1
EP2492273A1 EP11305190A EP11305190A EP2492273A1 EP 2492273 A1 EP2492273 A1 EP 2492273A1 EP 11305190 A EP11305190 A EP 11305190A EP 11305190 A EP11305190 A EP 11305190A EP 2492273 A1 EP2492273 A1 EP 2492273A1
Authority
EP
European Patent Office
Prior art keywords
gallium
substrate
precursor
deposition
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11305190A
Other languages
German (de)
English (en)
Inventor
Christophe Lachaud
Andreas Zauner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Priority to EP11305190A priority Critical patent/EP2492273A1/fr
Publication of EP2492273A1 publication Critical patent/EP2492273A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides

Definitions

  • Gallium is a rare metal which is most commonly recovered from the zinc-sulfide mineral sphalerite. Despite its rarity, gallium is used in multitude of technical applications from electronic to photovoltaic and optical devices. Gallium is dominantly used in gallium tin oxide layers (GaTO) for flat panel displays, copper- gallium -selenide (CGaS) type of solar cells, indium-gallium-nitride (InGaN) as used for LEDs; blue-ray lasers and InGaP for optoelectronic devices. In contrast to GaTO and CGaS that are mainly deposited by PVD, InGaN is mainly deposited by metal-organic chemical vapor deposition (MOCVD).
  • MOCVD metal-organic chemical vapor deposition
  • gallium can also be used for other applications.
  • the usage of Ga 2 S 3 to replace CdS in a photovoltaic CGaS based stack: CGaS/CdS/ZnO/ZnO:Al to obtain a better cell efficiency is already known.
  • Gallium is also reported to be used in phase-change materials (PCM) such as Ge 2 Sb 2 Te 5 (GST), to form gallium containing GST alloys to improve PCM characteristics such as data retention.
  • PCM phase-change materials
  • GST Ge 2 Sb 2 Te 5
  • Ga-Ge-Te Ga-Ge-Te
  • GaST Ga-Sb-Te
  • AgGaSbTe AgGaSbTe
  • Ga 2 Se 3 might be used for PCM fabrication. It is known that Ga 2 Se 3 has a wider variation in electrical resistivity in comparison with the previous Ge 2 Sb 2 Te 5 and therefore could be an alternative to GST.
  • MOCVD and ALD are common techniques to deposit thin films that can also be used for GST depositions. These techniques require ideally stable and volatile precursors. Concerning metal precursors several sources of metal are described in literature:
  • the invention relates to compounds of formula (I): [(R a )(R b )Ga(NR c R d )] 2 , wherein:
  • the invention concerns compounds as defined above wherein Ra and Rb are a methyl group.
  • the invention concerns compounds as defined above wherein Rc and Rd which may be identical or different are independently chosen between methyl and ethyl.
  • the invention concerns the compounds:
  • the invention concerns a method for forming a gallium containing thin film on a substrate comprising at least the steps of:
  • the invention concerns a method as defined above further comprising the step:
  • the invention concerns a method of manufacturing a semiconductor structure, comprising the steps of the method defined above, wherein the substrate is a semiconductor substrate.
  • the invention concerns a method of manufacturing a photovoltaic structure, comprising the steps of the method defined above, wherein the substrate is a photovoltaic substrate.
  • the invention concerns the use of at least one compound as defined above for the manufacturing of phase change materials (PCM).
  • PCM phase change materials
  • the new gallium metal-organic compounds present at least the following features:
  • the present invention introduces the using of a low melting point, volatile and thermally stable gallium compounds to deposit gallium containing thin films by either ALD process.
  • the family of gallium precursor of the present invention can be used for the deposition of gallium containing thin films by (MO)CVD (Metal-Organic Chemical Vapor Deposition) and derivatives.
  • MO Metal-Organic Chemical Vapor Deposition
  • novel metal-organic compounds could be used in various applications fields such as electronic, photovoltaic, optoelectronic devices.
  • the gallium nitride is deposited at 550°C on a sapphire substrate using [Me 2 Ga(NEtMe)]2 and NH 3 as reactive gas.
  • the precursor is stored into canisters and sublimed at 70°C.
  • N 2 is used as carrier gas.
  • the precursor and reactive gas are simultaneously introduced into the reactor. A film of gallium nitride film is obtained.
  • the gallium nitride is deposited at 500°C on a sapphire substrate using [Me 2 Ga(NEtMe)] 2 and ozone as reactive gas.
  • the precursor is stored into canisters and sublimed at 70°C.
  • N 2 is used as carrier gas.
  • the precursor and reactive gas are simultaneously introduced into the reactor. A film of gallium oxide is obtained.
  • Figure 1 shows that the precursor is thermally stable at least until 230°C; and Figure 2 shows that it presents sufficient volatility for vapor phase distribution: 1100 Pa (8 Torr) at 100°C.
  • [Me 2 Ga(NEtMe)] 2 is thermally stable and has a good volatility at the same time in addition of the fact that it is not a pyrophoric compound.
  • a sampling is performed in a glovebox under argon with a controlled level of oxygen and moisture (below 5 ppm). 250mg of powder are placed in a small glass crystallizer. The crystallizer is then placed in a leak proof screw cap jar during the transfer from the glovebox to a fume hood. The screw cap jar is opened under the fume hood and the crystallizer with the powder in placed directly in contact with air. No fumes are seen but there are some odours of amina (HNMe2). After 1 min, some drops of water are deposited directly on the product. Some bubbles are seen on the powder but without violent reaction.
  • HNMe2 amina

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
EP11305190A 2011-02-23 2011-02-23 Dépôt de films minces contenant du gallium au moyen d'un précurseur de gallium alkylamide Withdrawn EP2492273A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11305190A EP2492273A1 (fr) 2011-02-23 2011-02-23 Dépôt de films minces contenant du gallium au moyen d'un précurseur de gallium alkylamide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11305190A EP2492273A1 (fr) 2011-02-23 2011-02-23 Dépôt de films minces contenant du gallium au moyen d'un précurseur de gallium alkylamide

Publications (1)

Publication Number Publication Date
EP2492273A1 true EP2492273A1 (fr) 2012-08-29

Family

ID=44587736

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11305190A Withdrawn EP2492273A1 (fr) 2011-02-23 2011-02-23 Dépôt de films minces contenant du gallium au moyen d'un précurseur de gallium alkylamide

Country Status (1)

Country Link
EP (1) EP2492273A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10752992B2 (en) 2017-09-20 2020-08-25 Kojundo Chemical Laboratory Co., Ltd. Atomic layer deposition method of metal-containing thin film
CN112789367A (zh) * 2018-10-04 2021-05-11 株式会社Adeka 用于原子层沉积法的薄膜形成用原料、薄膜形成用原料、薄膜的制造方法及化合物
WO2022266449A1 (fr) * 2021-06-18 2022-12-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Précurseurs de gallium pour le dépôt de films d'oxyde contenant du gallium

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990010726A1 (fr) * 1989-03-09 1990-09-20 MERCK Patent Gesellschaft mit beschränkter Haftung Utilisation de composes organo-metalliques pour la deposition de couches minces en phase gazeuse
US5003092A (en) * 1989-06-02 1991-03-26 The Research Foundation Of State University Of Ny Use of R2 MR' to prepare semiconductor and ceramic precursors
US5068370A (en) * 1990-06-08 1991-11-26 The United States Of America As Represented By The Secretary Of The Navy Monomeric organometallic compounds and method of preparing same
WO1993022473A1 (fr) * 1992-04-30 1993-11-11 Sgs Mochem Products Gmbh Application de composes organometalloïdiques pour la deposition de l'element metalloïdique sur les substrats
KR100191737B1 (ko) * 1996-05-01 1999-06-15 이서봉 규소 기질 위에 질화갈륨 막을 형성하는 방법
US20040062283A1 (en) * 2002-09-30 2004-04-01 Tetsuya Takeuchi System and method for fabricating efficient semiconductor lasers via use of precursors having a direct bond between a group III atom and a nitrogen atom

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990010726A1 (fr) * 1989-03-09 1990-09-20 MERCK Patent Gesellschaft mit beschränkter Haftung Utilisation de composes organo-metalliques pour la deposition de couches minces en phase gazeuse
US5003092A (en) * 1989-06-02 1991-03-26 The Research Foundation Of State University Of Ny Use of R2 MR' to prepare semiconductor and ceramic precursors
US5068370A (en) * 1990-06-08 1991-11-26 The United States Of America As Represented By The Secretary Of The Navy Monomeric organometallic compounds and method of preparing same
WO1993022473A1 (fr) * 1992-04-30 1993-11-11 Sgs Mochem Products Gmbh Application de composes organometalloïdiques pour la deposition de l'element metalloïdique sur les substrats
KR100191737B1 (ko) * 1996-05-01 1999-06-15 이서봉 규소 기질 위에 질화갈륨 막을 형성하는 방법
US20040062283A1 (en) * 2002-09-30 2004-04-01 Tetsuya Takeuchi System and method for fabricating efficient semiconductor lasers via use of precursors having a direct bond between a group III atom and a nitrogen atom

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ALEXEY Y. TIMOSHKIN ET AL: "DFT Modeling of Chemical Vapor Deposition of GaN from Organogallium Precursors. 2. Structures of the Oligomers and Thermodynamics of the Association Processes +", THE JOURNAL OF PHYSICAL CHEMISTRY A, vol. 105, no. 13, 1 April 2001 (2001-04-01), pages 3249 - 3258, XP055008151, ISSN: 1089-5639, DOI: 10.1021/jp002380g *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; KIM, YUN SU ET AL: "Process for the preparation of gallium nitride film on silicon substrate", XP002660006, retrieved from STN Database accession no. 2004:853161 *
GERALD LINTI ET AL: "Zur Chemie des Galliums. 10. N-Trimethylsilyl-substituierte Aminogallane", ZEITSCHRIFT F R ANORGANISCHE UND ALLGEMEINE CHEMIE, vol. 623, no. 1-6, 1 January 1997 (1997-01-01), pages 531 - 538, XP055007985, ISSN: 0044-2313, DOI: 10.1002/zaac.19976230183 *
K. M. WAGGONER ET AL: "Synthesis and characterization of the monomeric gallium monoamides tert-Bu2GaN(R)SiPh3 (R = tert-Bu, 1-adamantyl), Trip2MN(H)Dipp (M = Al, Ga; Trip = 2,4,6-iso-Pr3C6H2; Dipp = 2,6-iso-Pr2C6H3), and Trip2GaNPh2", INORGANIC CHEMISTRY, vol. 32, no. 11, 1 May 1993 (1993-05-01), pages 2557 - 2561, XP055007986, ISSN: 0020-1669, DOI: 10.1021/ic00063a057 *
O. T. BEACHLEY ET AL: "Synthesis and Characterization of Monomeric Organogallium-Nitrogen Compounds, Et 2 GaNMe[C 6 H 2 (2,4,6-t-Bu) 3 ], Me 2 GaNMe[C 6 H 2 (2,4,6-t-Bu) 3 ], MeGa{NH[C 6 H 2 (2,4,6-t-Bu) 3 ]} 2 , and Ga{NH[C 6 H 2 (2,4,6-t-Bu) 3 ]} 3", ORGANOMETALLICS, vol. 20, no. 5, 1 March 2001 (2001-03-01), pages 945 - 949, XP055007983, ISSN: 0276-7333, DOI: 10.1021/om001050f *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10752992B2 (en) 2017-09-20 2020-08-25 Kojundo Chemical Laboratory Co., Ltd. Atomic layer deposition method of metal-containing thin film
CN112789367A (zh) * 2018-10-04 2021-05-11 株式会社Adeka 用于原子层沉积法的薄膜形成用原料、薄膜形成用原料、薄膜的制造方法及化合物
WO2022266449A1 (fr) * 2021-06-18 2022-12-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Précurseurs de gallium pour le dépôt de films d'oxyde contenant du gallium
TWI831250B (zh) * 2021-06-18 2024-02-01 法商液態空氣喬治斯克勞帝方法研究開發股份有限公司 用於沈積含鎵氧化物膜的鎵先質

Similar Documents

Publication Publication Date Title
KR101065829B1 (ko) 비정질 ｇｅ／ｔｅ 증착 방법
KR101499260B1 (ko) 상 변화 메모리 재료의 저온 증착
TWI516632B (zh) 含ｖａ族元素之薄膜之原子層沈積用的前驅物之合成與使用
US9240319B2 (en) Chalcogenide-containing precursors, methods of making, and methods of using the same for thin film deposition
US20110262660A1 (en) Chalcogenide-containing precursors, methods of making, and methods of using the same for thin film deposition
JP6471371B2 (ja) モリブデンシルシクロペンタジエニル錯体、シリルアリル錯体、及び、薄膜堆積におけるその使用
US8802194B2 (en) Tellurium precursors for film deposition
KR101304753B1 (ko) 상변화 물질 형성 방법 및 상변화 메모리 회로 형성 방법
EP2492273A1 (fr) Dépôt de films minces contenant du gallium au moyen d'un précurseur de gallium alkylamide
KR101772478B1 (ko) 유기 13족 전구체 및 이를 이용한 박막 증착 방법
CN108431295B (zh) 形成含钴膜的组合物、其合成、以及在膜沉积中的用途
JP6941610B2 (ja) マンガン含有フィルム形成組成物、マンガン含有フィルム形成組成物の合成およびフィルム析出における使用
EP2492272A1 (fr) Déposition des films minces contenant d'indium utilisant des précurseurs alkylamide d'indium
EP2540733A1 (fr) Dépôt de films minces contenant de l'indium au moyen de nouveaux précurseurs de l'indium
EP2540732A1 (fr) Dépôt de films minces contenant du gallium au moyen de nouveaux précurseurs de gallium
JP2019056133A (ja) 金属薄膜の原子層堆積方法
JP2023544202A (ja) 蒸着用インジウム前駆体
WO2017116667A1 (fr) Compositions filmogènes à base de fer, leur synthèse et leur utilisation pour le dépôt de film
KR20150059129A (ko) 유기 14족 준금속 아자이드 화합물 및 이를 이용한 박막 증착 방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130301